Esteramines and derivatives from natural oil metathesis

ABSTRACT

Esteramine compositions and their derivatives are disclosed. The esteramines comprise a reaction product of a metathesis-derived C 10 -C 17  monounsaturated acid, octadecene-1,18-dioic acid, or their ester derivatives with a tertiary alkanolamine. Derivatives made by quaternizing, sulfonating, alkoxylating, sulfating, and/or sulfitating the esteramines are also disclosed. In one aspect, the ester derivative of the C 10 -C 17  monounsaturated acid or octadecene-1,18-dioic acid is a lower alkyl ester. In other aspects, the ester derivative is a modified triglyceride made by self-metathesis of a natural oil or an unsaturated triglyceride made by cross-metathesis of a natural oil with an olefin. The esteramines and derivatives are valuable for a wide variety of end uses, including cleaners, fabric treatment, hair conditioning, personal care (liquid cleansing products, conditioning bars, oral care products), antimicrobial compositions, agricultural uses, and oil field applications.

FIELD OF THE INVENTION

The invention relates to esteramine and derivative compositions thatoriginate from renewable resources, particularly natural oils and theirmetathesis products.

BACKGROUND OF THE INVENTION

“Esteramines” are typically ester reaction products of fatty acids,fatty esters, or triglycerides and a tertiary alkanolamine (e.g.,triethanolamine or N,N-dimethylethanolamine). While esteramines havevalue in and of themselves, they are more commonly quaternized to make“ester quats,” cationic surfactants that have utility in a wide range ofend-use applications, including fabric softening (see U.S. Pat. Nos.5,670,677; 5,750,492; 6,004,913; 6,737,392; and U.S. Pat. Appl. Publ.No. 2001/0036909), cosmetics (U.S. Pat. No. 6,914,146), hairconditioning (U.S. Pat. No. 5,939,059), detergent additives for fuel(U.S. Pat. No. 5,964,907), antimicrobial compositions (U.S. Pat. No.6,420,330), agricultural dispersants (U.S. Pat. Appl. Publ. No.2010/0016163), and enhanced oil recovery (U.S. Pat. No. 7,163,056).

The fatty acids or esters used to make esteramines and their derivativesare usually made by hydrolysis or transesterification of triglycerides,which are typically animal or vegetable fats. Consequently, the fattyportion of the acid or ester will typically have 6-22 carbons with amixture of saturated and internally unsaturated chains. Depending onsource, the fatty acid or ester often has a preponderance of C₁₆ to C₂₂component. For instance, methanolysis of soybean oil provides thesaturated methyl esters of palmitic (C₁₆) and stearic (C₁₈) acids andthe unsaturated methyl esters of oleic (C₁₈ mono-unsaturated), linoleic(C₁₈ di-unsaturated), and α-linolenic (C₁₈ tri-unsaturated) acids. Theunsaturation in these acids has either exclusively or predominantlycis-configuration.

Recent improvements in metathesis catalysts (see J. C. Mol, Green Chem.4 (2002) 5) provide an opportunity to generate reduced chain length,monounsaturated feedstocks, which are valuable for making detergents andsurfactants, from C₁₆ to C₂₂-rich natural oils such as soybean oil orpalm oil. Soybean oil and palm oil can be more economical than, forexample, coconut oil, which is a traditional starting material formaking detergents. As Professor Mol explains, metathesis relies onconversion of olefins into new products by rupture and reformation ofcarbon-carbon double bonds mediated by transition metal carbenecomplexes. Self-metathesis of an unsaturated fatty ester can provide anequilibrium mixture of starting material, an internally unsaturatedhydrocarbon, and an unsaturated diester. For instance, methyl oleate(methyl cis-9-octadecenoate) is partially converted to 9-octadecene anddimethyl 9-octadecene-1,18-dioate, with both products consistingpredominantly of the trans-isomer. Metathesis effectively isomerizes thecis-double bond of methyl oleate to give an equilibrium mixture of cis-and trans-isomers in both the “unconverted” starting material and themetathesis products, with the trans-isomers predominating.

Cross-metathesis of unsaturated fatty esters with olefins generates newolefins and new unsaturated esters that can have reduced chain lengthand that may be difficult to make otherwise. For instance,cross-metathesis of methyl oleate and 3-hexene provides 3-dodecene andmethyl 9-dodecenoate (see also U.S. Pat. No. 4,545,941). Terminalolefins are particularly desirable synthetic targets, and ElevanceRenewable Sciences, Inc. recently described an improved way to preparethem by cross-metathesis of an internal olefin and an α-olefin in thepresence of a ruthenium alkylidene catalyst (see U.S. Pat. Appl. Publ.No. 2010/0145086). A variety of cross-metathesis reactions involving anα-olefin and an unsaturated fatty ester (as the internal olefin source)are described. Thus, for example, reaction of soybean oil with propylenefollowed by hydrolysis gives, among other things, 1-decene, 2-undecenes,9-decenoic acid, and 9-undecenoic acid. Despite the availability (fromcross-metathesis of natural oils and olefins) of unsaturated fattyesters having reduced chain length and/or predominantlytrans-configuration of the unsaturation, esteramines and theirderivatives made from these feedstocks appear to be unknown. Moreover,esteramines and their derivatives have not been made from the C₁₈unsaturated diesters that can be made readily by self-metathesis of anatural oil.

In sum, traditional sources of fatty acids and esters used for makingesteramines and their derivatives generally have predominantly (orexclusively) cis-isomers and lack relatively short-chain (e.g., C₁₀ orC₁₂) unsaturated fatty portions. Metathesis chemistry provides anopportunity to generate precursors having shorter chains and mostlytrans-isomers, which could impart improved performance when theprecursors are converted to downstream compositions (e.g., insurfactants). New C₁₈ difunctional esteramines and derivatives are alsopotentially available from natural oil self-metathesis or C₁₀unsaturated acid or ester self-metathesis. In addition to an expandedvariety of precursors, the unsaturation present in the precursors allowsfor further functionalization, e.g., by sulfonation or sulfitation.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to esteramine compositions. Theesteramines comprise a reaction product of a metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives with a tertiary alkanolamine. The invention includesderivatives made by quaternizing, sulfonating, alkoxylating, sulfating,and/or sulfitating the esteramines. In one aspect, the ester derivativeof the C₁₀-C₁₇ monounsaturated acid or octadecene-1,18-dioic acid is alower alkyl ester. In other aspects, the ester derivative is a modifiedtriglyceride made by self-metathesis of a natural oil or an unsaturatedtriglyceride made by cross-metathesis of a natural oil with an olefin.Esteramines and their derivatives are valuable for a wide variety of enduses, including cleaners, fabric treatment, hair conditioning, personalcare (liquid cleansing products, conditioning bars, oral care products),antimicrobial compositions, agricultural uses, and oil fieldapplications.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the invention relates to esteramine compositions thatcomprise reaction products of a metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives with a tertiary alkanolamine.

The C₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioic acid, or theirester derivatives used as a reactant is derived from metathesis of anatural oil. Traditionally, these materials, particularly theshort-chain acids and derivatives (e.g., 9-decylenic acid or9-dodecylenic acid) have been difficult to obtain except in lab-scalequantities at considerable expense. However, because of the recentimprovements in metathesis catalysts, these acids and their esterderivatives are now available in bulk at reasonable cost. Thus, theC₁₀-C₁₇ monounsaturated acids and esters are conveniently generated bycross-metathesis of natural oils with olefins, preferably α-olefins, andparticularly ethylene, propylene, 1-butene, 1-hexene, 1-octene, and thelike. Self-metathesis of the natural oil or a C₁₀ acid or esterprecursor (e.g., methyl 9-decenoate) provides the C₁₈ diacid or diesterin optimal yield when it is the desired product.

Preferably, at least a portion of the C₁₀-C₁₇ monounsaturated acid has“Δ⁹” unsaturation, i.e., the carbon-carbon double bond in the C₁₀-C₁₇acid is at the 9-position with respect to the acid carbonyl. In otherwords, there are preferably seven carbons between the acid carbonylgroup and the olefin group at C9 and C10. For the C₁₁ to C₁₇ acids, analkyl chain of 1 to 7 carbons, respectively is attached to C10.Preferably, the unsaturation is at least 1 mole % trans-Δ⁹, morepreferably at least 25 mole % trans-Δ⁹, more preferably at least 50 mole% trans-Δ⁹, and even more preferably at least 80% trans-Δ⁹. Theunsaturation may be greater than 90 mole %, greater than 95 mole %, oreven 100% trans-Δ⁹. In contrast, naturally sourced fatty acids that haveΔ⁹ unsaturation, e.g., oleic acid, usually have ˜100% cis-isomers.

Although a high proportion of trans-geometry (particularly trans-Δ⁹geometry) may be desirable in the metathesis-derived esteramines andderivatives of the invention, the skilled person will recognize that theconfiguration and the exact location of the carbon-carbon double bondwill depend on reaction conditions, catalyst selection, and otherfactors. Metathesis reactions are commonly accompanied by isomerization,which may or may not be desirable. See, for example, G. Djigoué and M.Meier, Appl. Catal. A: General 346 (2009) 158, especially FIG. 3. Thus,the skilled person might modify the reaction conditions to control thedegree of isomerization or alter the proportion of cis- andtrans-isomers generated. For instance, heating a metathesis product inthe presence of an inactivated metathesis catalyst might allow theskilled person to induce double bond migration to give a lowerproportion of product having trans-Δ⁹ geometry.

An elevated proportion of trans-isomer content (relative to the usualall-cis configuration of the natural monounsaturated acid or ester)imparts different physical properties to esteramine compositions madefrom them, including, for example, modified physical form, meltingrange, compactability, and other important properties. These differencesshould allow formulators that use esteramines and ester quats greaterlatitude or expanded choice as they use the esteramines in cleaners,fabric treatment, personal care, agricultural uses, and other end uses.

Suitable metathesis-derived C₁₀-C₁₇ monounsaturated acids include, forexample, 9-decylenic acid (9-decenoic acid), 9-undecenoic acid,9-dodecylenic acid (9-dodecenoic acid), 9-tridecenoic acid,9-tetradecenoic acid, 9-pentadecenoic acid, 9-hexadecenoic acid,9-heptadecenoic acid, and the like, and their ester derivatives.

Usually, cross-metathesis or self-metathesis of the natural oil isfollowed by separation of an olefin stream from a modified oil stream,typically by distilling out the more volatile olefins. The modified oilstream is then reacted with a lower alcohol, typically methanol, to giveglycerin and a mixture of alkyl esters. This mixture normally includessaturated C₆-C₂₂ alkyl esters, predominantly C₁₆-C₁₈ alkyl esters, whichare essentially spectators in the metathesis reaction. The rest of theproduct mixture depends on whether cross- or self-metathesis is used.When the natural oil is self-metathesized and then transesterified, thealkyl ester mixture will include a C₁₈ unsaturated diester. When thenatural oil is cross-metathesized with an α-olefin and the productmixture is transesterified, the resulting alkyl ester mixture includes aC₁₀ unsaturated alkyl ester and one or more C₁₁ to C₁₇ unsaturated alkylester coproducts in addition to the glycerin by-product. The terminallyunsaturated C₁₀ product is accompanied by different coproducts dependingupon which α-olefin(s) is used as the cross-metathesis reactant. Thus,1-butene gives a C₁₂ unsaturated alkyl ester, 1-hexene gives a C₁₄unsaturated alkyl ester, and so on. As is demonstrated in the examplesbelow, the C₁₀ unsaturated alkyl ester is readily separated from the C₁₁to C₁₇ unsaturated alkyl ester and each is easily purified by fractionaldistillation. These alkyl esters are excellent starting materials formaking the inventive esteramine compositions.

Natural oils suitable for use as a feedstock to generate the C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives from self-metathesis or cross-metathesis with olefins arewell known. Suitable natural oils include vegetable oils, algal oils,animal fats, tall oils, derivatives of the oils, and combinationsthereof. Thus, suitable natural oils include, for example, soybean oil,palm oil, rapeseed oil, coconut oil, palm kernel oil, sunflower oil,safflower oil, sesame oil, corn oil, olive oil, peanut oil, cottonseedoil, canola oil, castor oil, tallow, lard, poultry fat, fish oil, andthe like. Soybean oil, palm oil, rapeseed oil, and mixtures thereof arepreferred natural oils.

Genetically modified oils, e.g., high-oleate soybean oil or geneticallymodified algal oil, can also be used. Preferred natural oils havesubstantial unsaturation, as this provides a reaction site for themetathesis process for generating olefins. Particularly preferred arenatural oils that have a high content of unsaturated fatty groupsderived from oleic acid. Thus, particularly preferred natural oilsinclude soybean oil, palm oil, algal oil, and rapeseed oil.

A modified natural oil, such as a partially hydrogenated vegetable oil,can be used instead of or in combination with the natural oil. When anatural oil is partially hydrogenated, the site of unsaturation canmigrate to a variety of positions on the hydrocarbon backbone of thefatty ester moiety. Because of this tendency, when the modified naturaloil is self-metathesized or is cross-metathesized with the olefin, thereaction products will have a different and generally broaderdistribution compared with the product mixture generated from anunmodified natural oil. However, the products generated from themodified natural oil are similarly converted to inventive esteraminecompositions.

An alternative to using a natural oil as a feedstock to generate theC₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives from self-metathesis or cross-metathesis with olefins is amonounsaturated fatty acid obtained by the hydrolysis of a vegetable oilor animal fat, or an ester or salt of such an acid obtained byesterification of a fatty acid or carboxylate salt, or bytransesterification of a natural oil with an alcohol. Also useful asstarting compositions are polyunsaturated fatty esters, acids, andcarboxylate salts. The salts can include an alkali metal (e.g., Li, Na,or K); an alkaline earth metal (e.g., Mg or Ca); a Group 13-15 metal(e.g., B, Al, Sn, Pb, or Sb), or a transition, lanthanide, or actinidemetal. Additional suitable starting compositions are described at pp.7-17 of PCT application WO 2008/048522, the contents of which areincorporated by reference herein.

The other reactant in the cross-metathesis reaction is an olefin.Suitable olefins are internal or α-olefins having one or morecarbon-carbon double bonds. Mixtures of olefins can be used. Preferably,the olefin is a monounsaturated C₂-C₁₀ α-olefin, more preferably amonounsaturated C₂-C₈ α-olefin. Preferred olefins also include C₄-C₉internal olefins. Thus, suitable olefins for use include, for example,ethylene, propylene, 1-butene, cis- and trans-2-butene, 1-pentene,isohexylene, 1-hexene, 3-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, and the like, and mixtures thereof.

Cross-metathesis is accomplished by reacting the natural oil and theolefin in the presence of a homogeneous or heterogeneous metathesiscatalyst. The olefin is omitted when the natural oil isself-metathesized, but the same catalyst types are generally used.Suitable homogeneous metathesis catalysts include combinations of atransition metal halide or oxo-halide (e.g., WOCI₄ or WCI₆) with analkylating cocatalyst (e.g., Me₄Sn). Preferred homogeneous catalysts arewell-defined alkylidene (or carbene) complexes of transition metals,particularly Ru, Mo, or W. These include first and second-generationGrubbs catalysts, Grubbs-Hoveyda catalysts, and the like.

Suitable alkylidene catalysts have the general structure:

M[X¹X²L¹L²(L³)_(n)]═C_(m)═C(R¹)R²

where M is a Group 8 transition metal, L¹, L², and L³ are neutralelectron donor ligands, n is 0 (such that L³ may not be present) or 1, mis 0, 1, or 2, X¹ and X² are anionic ligands, and R¹ and R² areindependently selected from H, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. Any two or more of X¹, X², L¹, L²,L³, R¹ and R² can form a cyclic group and any one of those groups can beattached to a support.

First-generation Grubbs catalysts fall into this category where m=n=0and particular selections are made for n, X¹, X², L¹, L², L³, R¹ and R²as described in U.S. Pat. Appl. Publ. No. 2010/0145086 (“the '086publication”), the teachings of which related to all metathesiscatalysts are incorporated herein by reference.

Second-generation Grubbs catalysts also have the general formuladescribed above, but L¹ is a carbene ligand where the carbene carbon isflanked by N, O, S, or P atoms, preferably by two N atoms. Usually, thecarbene ligand is party of a cyclic group. Examples of suitablesecond-generation Grubbs catalysts also appear in the '086 publication.

In another class of suitable alkylidene catalysts, L¹ is a stronglycoordinating neutral electron donor as in first- and second-generationGrubbs catalysts, and L² and L³ are weakly coordinating neutral electrondonor ligands in the form of optionally substituted heterocyclic groups.Thus, L² and L³ are pyridine, pyrimidine, pyrrole, quinoline, thiophene,or the like.

In yet another class of suitable alkylidene catalysts, a pair ofsubstituents is used to form a bi- or tridentate ligand, such as abiphosphine, dialkoxide, or alkyldiketonate. Grubbs-Hoveyda catalystsare a subset of this type of catalyst in which L² and R² are linked.Typically, a neutral oxygen or nitrogen coordinates to the metal whilealso being bonded to a carbon that is α-, β-, or γ-with respect to thecarbene carbon to provide the bidentate ligand. Examples of suitableGrubbs-Hoveyda catalysts appear in the '086 publication.

The structures below provide just a few illustrations of suitablecatalysts that may be used:

Heterogeneous catalysts suitable for use in the self- orcross-metathesis reaction include certain rhenium and molybdenumcompounds as described, e.g., by J. C. Mol in Green Chem. 4 (2002) 5 atpp. 11-12. Particular examples are catalyst systems that include Re₂O₇on alumina promoted by an alkylating cocatalyst such as a tetraalkyl tinlead, germanium, or silicon compound. Others include MoCl₃ or MoCl₅ onsilica activated by tetraalkyltins.

For additional examples of suitable catalysts for self- orcross-metathesis, see U.S. Pat. No. 4,545,941, the teachings of whichare incorporated herein by reference, and references cited therein.

The esteramines are made by reacting a metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives with a tertiary alkanolamine.

In one aspect, the ester derivative is a lower alkyl ester, especially amethyl ester. The lower alkyl esters are preferably generated bytransesterifying a metathesis-derived triglyceride. For example,cross-metathesis of a natural oil with an olefin, followed by removal ofunsaturated hydrocarbon metathesis products by stripping, and thentransesterification of the modified oil component with a lower alkanolunder basic conditions provides a mixture of unsaturated lower alkylesters. The unsaturated lower alkyl ester mixture can be used “as is” tomake an inventive esteramine mixture or it can be purified to isolateparticular alkyl esters prior to making esteramines.

In another aspect, the ester derivative to be reacted with the tertiaryalkanolamine is the metathesis-derived triglyceride discussed in thepreceding paragraph. Instead of transesterifying the metathesis-derivedtriglyceride with a lower alkanol to generate lower alkyl esters asdescribed above, the metathesis-derived triglyceride, following olefinstripping, is reacted directly with the tertiary alkanolamine to make aninventive esteramine mixture.

The skilled person will appreciate that “ester derivative” hereencompasses other acyl equivalents, such as acid chlorides, acidanhydrides, or the like, in addition to the lower alkyl esters andglyceryl esters discussed above.

Suitable tertiary alkanolamines have a tertiary amine group and from oneto three primary or secondary hydroxyl groups. In preferredalkanolamines, the tertiary nitrogen is attached to zero, one, or twoC₁-C₁₀ alkyl groups, preferably C₁-C₄ alkyl groups, and from one tothree hydroxyalkyl groups having from 2 to 4 carbons each, where thetotal number of alkyl and hydroxyalkyl groups is three. Suitablealkanolamines are well known and commercially available from BASF, DowChemical and other suppliers. They include, for example,triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine,N,N-dimethylpropanolamine, N,N-dimethylisopropanolamine,N-methyldiisopropanolamine, N,N-diethylethanolamine,triisopropanolamine, and the like, and mixtures thereof. Particularlypreferred alkanolamines are triethanolamine, N-methyldiethanolamine, andN,N-dimethylethanolamine, which are economical and readily available.

Suitable alkanolamines include alkoxylated derivatives of the compoundsdescribed above. Thus, for example, the alkanolamine used to make theesteramine can be a reaction product of an alkanolamine with 0.1 to 20moles of ethylene oxide or propylene oxide per mole of —OH groups in thealkanolamine.

The esteramines are made using a well-known process that provides aunique product mixture because of the unconventional starting mixture ofacid or ester derivatives. The reactants are typically heated, with orwithout a catalyst under conditions effective to esterify ortransesterify the starting acid or ester with the tertiary alkanolamine.The reaction temperature is typically within the range of 80° C. to 300°C., preferably from 150° C. to 200° C., and more preferably from 165° C.to 180° C.

The relative amounts of alkanolamine and ester or acid reactants useddepend on the desired stoichiometry and is left to the skilled person'sdiscretion. Preferably, however, the equivalent ratio of acyl groups (inthe metathesis-derived acid or ester derivative) to hydroxyl groups (inthe tertiary alkanolamine) is within the range of 0.1 to 3, preferablyfrom 0.3 to 1. As the examples below illustrate, the ratio is frequentlyabout 1 (see the preparation of C10-2 or C10-4), but lower acyl:hydroxylequivalent ratios are also common (see, e.g., the preparation of C10-6,acyl:OH=0.56).

Some esteramines have the formula:

(R¹)_(3-m)—N—[(CH₂)_(n)—(CHCH₃)_(z)—O—CO—R²]_(m)

wherein:R¹ is C₁-C₆ alkyl; R² is —C₉H₁₆—R³ or —C₁₆H₃₀—CO₂R⁴; R³ is hydrogen orC₁-C₇ alkyl; R⁴ is substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, polyoxyalkylene, glyceryl ester, or a mono- or divalentcation; m=1-3; n=1-4; z=0 or 1; and when z=0, n=2-4.

Preferably, R² is —(CH₂)₇—CH═CHR³ or —(CH₂)₇—CH═CH—(CH₂)₇—CO₂R⁴.

General Note Regarding Chemical Structures:

As the skilled person will recognize, products made in accordance withthe invention are typically mixtures of cis- and trans-isomers. Exceptas otherwise indicated, all of the structural representations providedherein show only a trans-isomer. The skilled person will understand thatthis convention is used for convenience only, and that a mixture of cis-and trans-isomers is understood unless the context dictates otherwise.(The “C18-” series of products in the examples below, for instance, arenominally 100% trans-isomers whereas the “Mix-” series are nominally80:20 trans-/cis-isomer mixtures.) Structures shown often refer to aprincipal product that may be accompanied by a lesser proportion ofother components or positional isomers. For instance, reaction productsfrom modified triglycerides are complex mixtures. As another example,sulfonation or sulfitation processes often give mixtures of sultones,alkanesulfonates, and alkenesulfonates, in addition to isomerizedproducts. Thus, the structures provided represent likely or predominantproducts. Charges may or may not be shown but are understood, as in thecase of amine oxide structures. Counterions, as in quaternizedcompositions, are not usually included, but they are understood by theskilled person from the context.

Some specific examples of C₁₀, C₁₂, C₁₄, and C₁₆-based esteraminesappear below:

Some specific examples of C₁₈-based esteramines:

The esteramine product mixture can be complex when the ester derivativereacted with the alkanolamine is a modified triglyceride made byself-metathesis of a natural oil and separation to remove olefins (see,e.g., the MTG and PMTG products described below) or an unsaturatedtriglyceride made by cross-metathesis of a natural oil and an olefin andseparation to remove olefins (see, e.g., the UTG and PUTG productsdescribed below). As is evident from the reaction schemes, the MTG andPMTG products include an unsaturated C₁₈ diesteramine as a principalcomponent, while the UTG and PUTG products include a C₁₀ unsaturatedesteramine component and one or more C₁₁ to C₁₇ unsaturated esteraminecomponents. (For example, with 1-butene as the cross-metathesisreactant, as illustrated, a C₁₂ unsaturated esteramine componentresults.) Other components of the product mixtures are glycerin andsaturated or unsaturated mono-, di-, or triesters that incorporate thealkanolamine. Despite the complexity, purification to isolate aparticular species is often neither economical nor desirable for goodperformance.

Thus, in one aspect, the esteramine is produced by reacting analkanolamine with a modified triglyceride made by self-metathesis of anatural oil. Self-metathesis of the natural oil provides a mixture ofolefins and a modified triglyceride that is enriched in a C₁₈unsaturated diester component along with C₁₆-C₁₈ saturated diesters. Theolefins are stripped out, usually with heat and reduced pressure. Whenthe self-metathesis product is reacted directly with the alkanolamine, acomplex mixture results in which hydroxyl groups of the alkanolaminecompletely or partially displace glycerin from the glyceryl esters toform esteramine functionalities. Representative esteramine productsbelow are made by reacting alkanolamines with MTG-0 (modifiedtriglyceride from soybean oil) or PMTG-0 (modified triglyceride frompalm oil). One example is the MTG 2:1 TEA ester:

In another aspect, the esteramine is produced by reacting analkanolamine with an unsaturated triglyceride made by cross-metathesisof a natural oil with an olefin. Cross-metathesis of the natural oil andolefin provides a mixture of olefins and an unsaturated triglyceridethat is rich in C₁₀ and C₁₂ unsaturated esters as well as C₁₆-C₁₈saturated esters. The olefins are stripped out, usually with heat andreduced pressure. When the cross-metathesis product is reacted with thealkanolamine, a complex mixture results in which hydroxyl groups of thealkanolamine completely or partially displace glycerin from the glycerylesters to form esteramine functionalities. Representative esteramineproducts below are made by reacting alkanolamines with UTG-0(unsaturated triglyceride from cross-metathesis of soybean oil and1-butene) or PUTG-0 (unsaturated triglyceride from cross-metathesis ofpalm oil with 1-butene). One example is the PUTG 2:1 TEA ester product:

The reaction to form the esteramines can be performed under a nitrogensparge or under vacuum to remove liberated alcohol. When glycerideesters are reactants, the liberated glycerin need not be removed fromthe product. The reaction is considered complete when the residualglyceride content of the product reaches the desired level.

The invention includes derivatives made by one or more of quaternizing,sulfonating, alkoxylating, sulfating, and sulfitating the esteramine.Methods for quaternizing tertiary amines are well known in the art.Quaternization of the esteramines is accomplished by warming them with aquaternizing agent such as an alkyl halide or dialkyl sulfate. Specificexamples include dimethylsulfate, methyl chloride, epichlorohydrin,benzyl chloride, alkali metal chloroacetates, and the like. Dimethylsulfate is particularly preferred. The reaction is generally performedat a temperature within the range of 30° C. to 150° C., preferably from65° C. to 100° C., or more preferably from 80° C. to 90° C. The amountof quaternizing agent used is typically 0.8 to 1.0 mole equivalentsbased on the tertiary nitrogen content. The reaction is deemed completewhen the free amine value is in the desired range as determined byperchloric acid titration. Suitable methods for quaternizing theesteramines are disclosed in U.S. Pat. Nos. 5,750,492; 5,783,534;5,939,059; and 6,004,913, the teachings of which are incorporated hereinby reference.

Examples of suitable C₁₀, C₁₂, C₁₄, and C₁₆-based quaternizedesteramines (“ester quats”):

Examples of suitable C₁₈-based ester quats:

An exemplary ester quat based on a PUTG-based esteramine mixture:

The esteramines and ester quats have unsaturation that can be sulfonatedor sulfitated if desired. Sulfonation is performed using well-knownmethods, including reacting the olefin with sulfur trioxide. Sulfonationmay optionally be conducted using an inert solvent. Non-limitingexamples of suitable solvents include liquid SO₂, hydrocarbons, andhalogenated hydrocarbons. In one commercial approach, a falling filmreactor is used to continuously sulfonate the olefin using sulfurtrioxide. Other sulfonating agents can be used with or without use of asolvent (e.g., chlorosulfonic acid, fuming sulfuric acid), but sulfurtrioxide is generally the most economical. The sultones that are theimmediate products of reacting olefins with SO₃, chlorosulfonic acid,and the like may be subsequently subjected to a hydrolysis reaction withaqueous caustic to afford mixtures of alkene sulfonates andhydroxyalkane sulfonates. Suitable methods for sulfonating olefins aredescribed in U.S. Pat. Nos. 3,169,142; 4,148,821; and U.S. Pat. Appl.Publ. No. 2010/0282467, the teachings of which are incorporated hereinby reference.

Sulfitation is accomplished by combining an olefin in water (and usuallya cosolvent such as isopropanol) with at least a molar equivalent of asulfitating agent using well-known methods. Suitable sulfitating agentsinclude, for example, sodium sulfite, sodium bisulfite, sodiummetabisulfite, or the like. Optionally, a catalyst or initiator isincluded, such as peroxides, iron, or other free-radical initiators.Typically, the reaction mixture is conducted at 15-100° C. until thereaction is reasonably complete. Suitable methods for sulfitatingolefins appear in U.S. Pat. Nos. 2,653,970; 4,087,457; 4,275,013, theteachings of which are incorporated herein by reference.

When the esteramine has hydroxyl functionality, it can also bealkoxylated, sulfated, or both using well-known techniques. Forinstance, a hydroxyl-terminated esteramine can be alkoxylated byreacting it with ethylene oxide, propylene oxide, or a combinationthereof to produce an alkoxylated alcohol. Alkoxylations are usuallycatalyzed by a base (e.g., KOH), but other catalysts such as doublemetal cyanide complexes (see U.S. Pat. No. 5,482,908) can also be used.The oxyalkylene units can be incorporated randomly or in blocks. Thehydroxyl-functional esteramine can be sulfated, with or without a prioralkoxylation, and neutralized to give an alcohol sulfate according toknown methods (see, e.g., U.S. Pat. No. 3,544,613, the teachings ofwhich are incorporated herein by reference).

The esteramines and their quaternized, sulfonated, alkoxylated,sulfated, and sulfitated derivatives can be incorporated into manycompositions for use as, for example, surfactants, emulsifiers,skin-feel agents, film formers, rheological modifiers, biocides, biocidepotentiators, solvents, release agents, and conditioners. Thecompositions find value in diverse end uses, such as personal care(liquid cleansing products, conditioning bars, oral care products),household products (liquid and powdered laundry detergents, liquid andsheet fabric softeners, hard and soft surface cleaners, sanitizers anddisinfectants), and industrial or institutional cleaners.

The esteramines and derivatives can be used in emulsion polymerizations,including processes for the manufacture of latex. They can be used assurfactants, wetters, dispersants, or solvents in agriculturalapplications, as inert ingredients in pesticides, or as adjuvants fordelivery of pesticides for crop protection, home and garden, andprofessional applications. The esteramines and derivatives can also beused in oil field applications, including oil and gas transport,production, stimulation and drilling chemicals, reservoir conformanceand enhancement uses, and specialty foamers. The compositions are alsovaluable as foam moderators or dispersants for the manufacture ofgypsum, cement wall board, concrete additives and firefighting foams.The compositions are used as coalescents for paints and coatings, and aspolyurethane-based adhesives.

In food and beverage processing, the esteramines and derivatives can beused to lubricate the conveyor systems used to fill containers. Whencombined with hydrogen peroxide, the esteramines and derivatives canfunction as low foaming disinfectants and sanitization agents, odorreducers, and as antimicrobial agents for cleaning and protecting foodor beverage processing equipment. In industrial, institutional andlaundry applications, the esteramines and derivatives, or theircombination with hydrogen peroxide, can be used to remove soil andsanitize and disinfect fabrics and as antimicrobial film-formingcompositions on hard surfaces.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

Feedstock Syntheses Preparation of Methyl 9-Decenoate (“C10-0”) andMethyl 9-Dodecenoate (“C12-0”)

The procedures of U.S. Pat. Appl. Publ. No. 2011/0113679, the teachingsof which are incorporated herein by reference, are used to generatefeedstocks C10-0 and C12-0 as follows:

Example 1A Cross-Metathesis of Soybean Oil and 1-Butene

A clean, dry, stainless-steel jacketed 5-gallon Parr reactor equippedwith a dip tube, overhead stirrer, internal cooling/heating coils,temperature probe, sampling valve, and relief valve is purged with argonto 15 psig. Soybean oil (SBO, 2.5 kg, 2.9 mol, Costco, M_(n)=864.4g/mol, 85 weight % unsaturation, sparged with argon in a 5-gal containerfor 1 h) is added to the Parr reactor. The reactor is sealed, and theSBO is purged with argon for 2 h while cooling to 10° C. After 2 h, thereactor is vented to 10 psig. The dip tube valve is connected to a1-butene cylinder (Airgas, CP grade, 33 psig headspace pressure, >99 wt.%) and re-pressurized to 15 psig with 1-butene. The reactor is againvented to 10 psig to remove residual argon. The SBO is stirred at 350rpm and 9-15° C. under 18-28 psig 1-butene until 3 mol 1-butene per SBOolefin bond are transferred into the reactor (˜2.2 kg 1-butene over 4-5h).

A toluene solution of[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlororuthenium(3-methyl-2-butenylidene)(tricyclohexylphosphine) (C827, Materia) isprepared in a Fischer-Porter pressure vessel by dissolving 130 mgcatalyst in 30 g of toluene (10 mol ppm per mol olefin bond of SBO). Thecatalyst mixture is added to the reactor via the reactor dip tube bypressurizing the headspace inside the Fischer-Porter vessel with argonto 50-60 psig. The Fischer-Porter vessel and dip tube are rinsed withadditional toluene (30 g). The reaction mixture is stirred for 2.0 h at60° C. and is then allowed to cool to ambient temperature while thegases in the headspace are vented.

After the pressure is released, the reaction mixture is transferred to around-bottom flask containing bleaching clay (Pure-Flo® B80 CG clay,product of Oil-Dri Corporation of America; 2% w/w SBO, 58 g) and amagnetic stir bar. The reaction mixture is stirred at 85° C. underargon. After 2 h, during which time any remaining 1-butene is allowed tovent, the reaction mixture cools to 40° C. and is filtered through aglass frit. An aliquot of the product mixture is transesterified with 1%w/w NaOMe in methanol at 60° C. By gas chromatography (GC), it contains:methyl 9-decenoate (22 wt. %), methyl 9-dodecenoate (16 wt. %), dimethyl9-octadecenedioate (3 wt. %), and methyl 9-octadecenoate (3 wt. %).

The results compare favorably with calculated yields for a hypotheticalequilibrium mixture: methyl 9-decenoate (23.4 wt. %), methyl9-dodecenoate (17.9 wt/%), dimethyl 9-octadecenedioate (3.7 wt. %), andmethyl 9-octadecenoate (1.8 wt. %).

Example 1B

The procedure of Example 1A is generally followed with 1.73 kg SBO and 3mol 1-butene/SBO double bond. An aliquot of the product mixture istransesterified with sodium methoxide in methanol as described above.The products (by GC) are: methyl 9-decenoate (24 wt. %), methyl9-dodecenoate (18 wt. %), dimethyl 9-octadecenedioate (2 wt. %), andmethyl 9-octadecenoate (2 wt. %).

Example 1C

The procedure of Example 1A is generally followed with 1.75 kg SBO and 3mol 1-butene/SBO double bond. An aliquot of the product mixture istransesterified with sodium methoxide in methanol as described above.The products (by GC) are: methyl 9-decenoate (24 wt. %), methyl9-dodecenoate (17 wt. %), dimethyl 9-octadecenedioate (3 wt. %), andmethyl 9-octadecenoate (2 wt. %).

Example 1D

The procedure of Example 1A is generally followed with 2.2 kg SBO and 3mol 1-butene/SBO double bond. Additionally, the toluene used to transferthe catalyst (60 g) is replaced with SBO. An aliquot of the productmixture is transesterified with sodium methoxide in methanol asdescribed above. The products (by GC) are: methyl 9-decenoate (25 wt.%), methyl 9-dodecenoate (18 wt. %), dimethyl 9-octadecenedioate (3 wt.%), and methyl 9-octadecenoate (1 wt. %).

Example 1E Separation of Olefins from Modified Triglyceride

A 12-L round-bottom flask equipped with a magnetic stir bar, heatingmantle, and temperature controller is charged with the combined reactionproducts from Examples 1A-1D (8.42 kg). A cooling condenser with avacuum inlet is attached to the middle neck of the flask and a receivingflask is connected to the condenser. Volatile hydrocarbons (olefins) areremoved from the reaction product by vacuum distillation. Pottemperature: 22° C.-130° C.; distillation head temperature: 19° C.-70°C.; pressure: 2000-160 μtorr. After removing the volatile hydrocarbons,5.34 kg of non-volatile residue remains. An aliquot of the non-volatileproduct mixture is transesterified with sodium methoxide in methanol asdescribed above. The products (by GC) are: methyl 9-decenoate (32 wt.%), methyl 9-dodecenoate (23 wt. %), dimethyl 9-octadecenedioate (4 wt.%), and methyl 9-octadecenoate (5 wt. %). This mixture is also called“UTG-0.” (An analogous product made from palm oil is called “PUTG-0.”)

Example 1F Methanolysis of Modified Triglyceride

A 12-L round-bottom flask fitted with a magnetic stir bar, condenser,heating mantle, temperature probe, and gas adapter is charged withsodium methoxide in methanol (1% w/w, 4.0 L) and the non-volatileproduct mixture produced in Example 1E (5.34 kg). The resultinglight-yellow heterogeneous mixture is stirred at 60° C. After 1 h, themixture turns homogeneous and has an orange color (pH=11). After 2 h ofreaction, the mixture is cooled to ambient temperature and two layersform. The organic phase is washed with aqueous methanol (50% v/v, 2×3L), separated, and neutralized by washing with glacial acetic acid inmethanol (1 mol HOAc/mol NaOMe) to pH=6.5. Yield: 5.03 kg.

Example 1G Isolation of Methyl Ester Feedstocks

A 12-L round-bottom flask fitted with a magnetic stirrer, packed column,and temperature controller is charged with the methyl ester mixtureproduced in example 1F (5.03 kg), and the flask is placed in a heatingmantle. The glass column is 2″×36″ and contains 0.16″ Pro-Pak™stainless-steel saddles (Cannon Instrument Co.). The column is attachedto a fractional distillation head to which a 1-L pre-weighed flask isfitted for collecting fractions. Distillation is performed under vacuum(100-120 μtorr). A reflux ratio of 1:3 is used to isolate methyl9-decenoate (“C10-0”) and methyl 9-dodecenoate (“C12-0”). Samplescollected during the distillation, distillation conditions, and thecomposition of the fractions (by GC) are shown in Table 1. A refluxratio of 1:3 refers to 1 drop collected for every 3 drops sent back tothe distillation column. Combining appropriate fractions yields methyl9-decenoate (1.46 kg, 99.7% pure) and methyl 9-dodecenoate (0.55kg, >98% pure).

TABLE 1 Isolation of C10-0 and C12-0 by Distillation Head Distillationtemp. Pot temp. Vacuum Weight C10-0 C12-0 Fractions # (° C.) (° C.)(μtorr) (g) (wt %) (wt %) 1 40-47 104-106 110 6.8 80 0 2 45-46 106 11032.4 99 0 3 47-48 105-110 120 223.6 99 0 4 49-50 110-112 120 283 99 0 550 106 110 555 99 0 6 50 108 110 264 99 0 7 50 112 110 171 99 0 8 51 114110 76 97 1 9 65-70 126-128 110 87 47 23 10 74 130-131 110 64 0 75 11 75133 110 52.3 0 74 12 76 135-136 110 38 0 79 13 76 136-138 100 52.4 0 9014 76 138-139 100 25.5 0 85 15 76-77 140 110 123 0 98 16 78 140 100 4260 100Preparation of Fatty Acids from Methyl Esters

Methyl esters C10-0, C12-0, and Mix-0 are converted to their respectivefatty acids (C10-36, C12-39, and Mix-67) as follows.

Potassium hydroxide/glycerin solution (16-17 wt. % KOH) is added to aflask equipped with an overhead stirrer, thermocouple, and nitrogensparge, and the solution is heated to ˜100° C. The methyl ester is thenadded to the KOH/glycerine solution. An excess of KOH (2-4 moles KOH permole of methyl ester) is used; for monoesters the mole ratio is about 2,and for diesters about 4. The reaction temperature is raised to 140° C.and heating continues until gas chromatography analysis indicatescomplete conversion. Deionized water is added so that the weight ratioof reaction mixture to water is about 1.5. The solution is heated to 90°C. to melt any fatty acid salt that may have solidified. Sulfuric acid(30% solution) is added and mixed well to convert the salt to the freefatty acid, and the layers are allowed to separate. The aqueous layer isdrained, and the fatty acid layer is washed with water until the aqueouswashes are neutral. The crude fatty acids are used “as is” for makingsome of the esteramines.

Analysis of Unreacted Amines in Esteramines

Several grams of esteramine are dissolved in 100 mL of a 70/30 (vol/vol)mixture of toluene and isopropanol and this solution is extracted withone 50-mL portion and two 25-mL portions of 20% aqueous NaCl. Thecombined aqueous layers are then titrated with 0.1 N aqueous HCl. Theamount of extracted amine is interpreted as being the amount ofunreacted amine. It is calculated from the titration endpoint volume andthe molecular weight of the starting amine used to prepare theesteramine composition.

C10-2: C10 TEA Ester

Fatty acid C10-36 (176.7 g, 0.984 mol), base catalyst, andtriethanolamine (49.0 g, 0.328 mol) are charged to a 4-neck flask undera blanket of nitrogen. A subsurface sparge of nitrogen (200 mL/min) ismaintained. The mixture is stirred (170 rpm) and heated without a vacuumto 185° C. and held for 21 h. Free fatty acid content is found bytitration to be 0.078 meq/g. The reaction temperature is increased to190° C. under vacuum (50 mm Hg) and heating continues for an additional4 h. After cooling, the esteramine product, C10-2, has a fatty acidcontent of 0.0651 meq/g and an unreacted triethanolamine value of 0.77%.

C10-4: C10 MDEA Ester

Fatty acid C10-36 (168.5 g, 0.939 mol), base catalyst, andN-methyldiethanolamine (55.9 g, 0.469 mol) are charged to a 4-neck flaskunder a blanket of nitrogen. A subsurface sparge of nitrogen (200mL/min) is maintained. The mixture is stirred (170 rpm) and heatedwithout a vacuum to 185° C. and held for 20 h. Free fatty acid contentis found by titration: 0.133 meq/g. Reaction temperature is reduced to180° C. (200 mm Hg) and heating continues for another 8 h. Fatty acidcontent: 0.123 meq/g. Additional N-methyldiethanolamine (7.2 g) isadded, and heating continues at 180° C. (200 mm Hg) for another 3 h.After cooling, the esteramine product, C10-4, has a fatty acid contentof 0.0649 meq/g and an unreacted N-methyldiethanolamine value of 1.11%.

C10-6: C10 DMEA Ester

Fatty acid C10-36 (153.7 g, 0.890 mol) and N,N-dimethylethanolamine(142.7 g, 1.60 mol) are charged to a flask equipped with heating mantle,temperature controller, mechanical agitator, nitrogen sparge, five-plateOldershaw column, and condenser. The mixture is gradually heated to 180°C. while the overhead distillate temperature is kept below 105° C. Afterthe reaction mixture temperature reaches 180° C., it is held at thistemperature overnight. Free fatty acid content by ¹H NMR: 5%(essentially complete). The mixture is cooled to 90° C. and the column,condenser, and nitrogen sparge are removed. Vacuum is applied inincrements to 20 mm Hg over ˜1 h, held at held at 20 mm Hg for 0.5 h,then improved to full vacuum for 1.5 h. The esteramine product, C10-6,has an unreacted dimethylethanolamine value of 0.41%. Purity isconfirmed by a satisfactory ¹H NMR spectrum.

C12-2: C12 TEA Ester

Methyl ester C12-0 (193.9 g, 0.912 mol), base catalyst, andtriethanolamine (45.5 g, 0.305 mol) are charged to a 4-neck flask undera blanket of nitrogen. A subsurface sparge of nitrogen (200 mL/min) ismaintained. The mixture is stirred (170 rpm) and heated without a vacuumto 165° C. and held for 16 h. ¹H NMR indicates essentially completereaction with a trace of unreacted methyl ester. After cooling, theesteramine product, C12-2, has an unreacted triethanolamine value of0.06%.

C12-4: C12 MDEA Ester

Methyl ester C12-0 (185.9 g, 0.875 mol), base catalyst, andN-methyldiethanolamine (54.9 g, 0.460 mol) are charged to a 4-neck flaskunder a blanket of nitrogen. A subsurface sparge of nitrogen (200mL/min) is maintained. The mixture is stirred (170 rpm) and heatedwithout a vacuum to 165° C. and held for 16 h. The temperature isincreased to 170° C. (at 200 mm Hg) and heating continues for 3 h. Aftercooling, the esteramine product, C12-4, has an unreactedN-methyldiethanolamine value of 3.22%. Purity is confirmed by asatisfactory ¹H NMR spectrum.

C12-6: C12 DMEA Ester

Fatty acid C12-39 (187.2 g, 0.917 mol) and N,N-dimethylethanolamine(147.1 g, 1.65 mol) are charged to a flask equipped with heating mantle,temperature controller, mechanical agitator, nitrogen sparge, five-plateOldershaw column, and condenser. The mixture is gradually heated to 180°C. while the overhead distillate temperature is kept below 105° C. Afterthe reaction mixture temperature reaches 180° C., it is held at thistemperature overnight. Free fatty acid content: 1.59%. The mixture iscooled to 90° C. and the column, condenser, and nitrogen sparge areremoved. After the usual vacuum stripping, the esteramine product,C12-6, has an unreacted dimethylethanolamine value of 0.084%. Purity isconfirmed by a satisfactory ¹H NMR spectrum.

Preparation of Methyl 9-Hexadecenoate (“C16-0”) Feedstock

The procedures of Example 1A is generally followed except that 1-octeneis cross-metathesized with soybean oil instead of 1-butene. Combinedreaction products are then stripped as described in Example 1E to removethe more volatile unsaturated hydrocarbon fraction from the modified oilfraction. The procedure of Example 1F is used to convert the modifiedoil fraction to a methyl ester mixture that includes methyl9-hexadecenoate. Fractional distillation at reduced pressure is used toisolate the desired product, methyl 9-hexadecenoate from other methylesters.

C16-3: C16 Fatty Acid

Potassium hydroxide (20 g) and glycerol (112 g) are added to around-bottom flask equipped with a Dean-Stark trap. The mixture isstirred mechanically and heated to 100° C. under nitrogen untilhomogeneous. Unsaturated methyl ester C16-0 (80 g) is added and themixture is heated to 120° C., then held for 3 h. Gas chromatographyindicates a complete conversion to the desired acid. Deionized water(100 g) and 30% aq. sulfuric acid solution (132 g) are added to thereaction mixture. The layers are separated and the organic phase iswashed with deionized water (3×220 mL) at 60° C. Short-path distillationis performed to remove water (100° C., full vacuum, 2 h). The product,C16-3, obtained in 92% yield, is analyzed: acid value: 219.7 mg KOH/g;moisture: 0.1%; isomer ratio: 18.8 cis-181.2 trans-. ¹H NMR (DMSO), δ(ppm): 5.36 (CH═CH); 2.34 (—CH₂—C(O)—OH).

C16-6: C16 MDEA Ester

The procedure used to make C12-4 is generally followed using fattymethyl ester C16-0 (162.5 g) and N-methyldiethanolamine (35.7 g). Theproduct, C16-6, has an unreacted N-methyldiethanolamine value of 0.88%and gives a satisfactory ¹H NMR spectrum.

Ester Quat Formation from C10 and C12 Esteramines

Each of the esteramines prepared as described above is quaternized asfollows. Table 2 summarizes the products, amount of dimethyl sulfate(“DMS,” quaternizing agent), reaction time, temperature, and amount ofisopropyl alcohol (“IPA”) solvent. The amount of DMS used for allreactions is determined by perchloric acid titration (“PAT” value) ofthe esteramine.

The esteramine is charged to a round-bottom flask equipped with a refluxcondenser, thermocouple/heating mantle, and nitrogen inlet. The sampleis heated to 65° C. if IPA is used to help solubilize the esteramine;otherwise, it is heated to 75-80° C. DMS is added dropwise via anaddition funnel. Temperature is kept at or below 70° C. if IPA isincluded and at or below 85° C. if it is not used. After the DMS isadded, the temperature is increased to 70° C. (if IPA is included) andstirred for 2-3 h; otherwise, the temperature is raised to 85° C. andstirred for 1 h. The reaction is considered complete if the PAT valueindicates <5% quaternizable amine remaining based on the original PATvalue of the esteramine. IPA (˜10 wt. %) is added (unless addedpreviously) to help eliminate residual DMS. The reaction mixture is alsoheated at 80-85° C. for 1 h to ensure complete DMS removal; contents arealso tested with a Dräger apparatus for residual DMS.

TABLE 2 C10 and C12 Ester Quat Synthesis % Quat Rxn. by Esteramine DMSTime Temp. PAT IPA Ester Quat Product (g) (g) (h) (° C.) Value (g)

  C10-3: C10 TEA Ester Quat 147.5 30.5 3 70 98.5 20.0

  C10-5: C10 MDEA Ester Quat 148.9 46.5 1 85 98.7 22.0

  C10-7: C10 DMEA Ester Quat  98.9 49.6 3 70 98.2 26.2

  C12-3: C12 TEA Ester Quat 154.0 26.6 3 70 98.0 20.0

  C12-5: C12 MDEA Ester Quat 162.4 38.6 1 85 98.4 23.0

  C12-7: C12 DMEA Ester Quat  99.8 44.6 3 70 98.8 24.0

C16-7: C16 MDEA Ester Quat

MDEA ester C16-6 (127.8 g) is placed in a round-bottom flask equippedwith a condenser, thermocouple, heating mantle, and nitrogen inlet. Thecontents are heated to 80° C. Dimethyl sulfate (27.7 g) is added viaaddition funnel. The amount of DMS is added to achieve >95%quaternization as determined from the perchloric acid titration (PAT)value. After the DMS addition, the temperature is raised to 85° C. Twohours after the DMS addition is complete, the percent quaternization is˜97%. Isopropyl alcohol (17.0 g) is added and the temperature is kept at85° C. After 1 h, the mixture is cooled to room temperature. Theproduct, C16-7, is removed and tested with a Dräger apparatus forresidual DMS.

Feedstock Synthesis Preparation of Dimethyl 9-Octadecene-1,18-dioate(“Mix-0” or “C18-0”

Eight samples of methyl 9-dodecenoate (10.6 g each, see Table 3) arewarmed to 50° C. and degassed with argon for 30 min. A metathesiscatalyst([1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(3-methyl-2-butenylidene)-(tricyclohexylphosphine), product of Materia)is added to the methyl 9-dodecenoate (amount indicated in Table 3) andvacuum is applied to provide a pressure of <1 mm Hg. The reactionmixture is allowed to self-metathesize for the time reported. Analysisby gas chromatography indicates that dimethyl 9-octadecene-1,18-dioateis produced in the yields reported in Table 3. “Mix-0” is an 80:20trans-/cis-isomer mixture obtained from the reaction mixture.Crystallization provides the all-trans-isomer feed, “C18-0.”

TABLE 3 Self-Metathesis of Methyl 9-Dodecanoate Catalyst LoadingReaction C18-0 Sample (ppm mol/mol)* Time (h) (GC Area %) A 100 3 83.5 B50 3 82.5 C 25 3 83.0 D 10 3 66.2 E 15 4 90.0 F 13 4 89.9 G 10 4 81.1 H5 4 50.9 *ppm mol catalyst/mol methyl 9-dodecenoate

Esteramines are prepared from the C18 diesters, “Mix-0” or “Mix-0-2”(80:20 trans-/cis-mixtures) or “C18-0” (100% trans-) as described below.

MIX-3: C18 TEA Ester (2:1) Mix (80:20 Trans-/Cis-)

Methyl ester Mix-O-2 (246.0 g, 0.720 mol), base catalyst, andtriethanolamine (107.4 g, 0.720 mol) are charged to a 4-neck flaskequipped with a distillation head and condenser. The contents are heatedto 80° C., then to 135° C., under a nitrogen flow (150 mL/min). Methanoldistills as the reaction proceeds, and the temperature is graduallyincreased to 175° C. over 2 h. The nitrogen flow is then directed belowthe liquid surface. After 3.5 h at 175° C., the mixture is cooled. Themethanol collected is 77.4% of the theoretical amount. The mixture hasbecome viscous and the reaction is deemed complete. The esteramineproduct, Mix-3, has an unreacted triethanolamine value of 3.46%.

MIX-5: C18 TEA Ester (1:1) Mix (80:20 Trans-/Cis-)

Methyl ester Mix-0-2 (167.0 g, 0.489 mol), base catalyst, andtriethanolamine (145.9 g, 0.978 mol) are charged to a 4-neck flask undera blanket of nitrogen. A subsurface sparge of nitrogen (200 mL/min) ismaintained. The mixture is stirred (170 rpm) and heated without a vacuumto 150° C. and held for 1 h, after which the temperature is increased to180° C. and held for 22 h. The temperature is reduced to 175° C. (400 mmHg) for another 4 h. After cooling, the esteramine product, Mix-5, hasan unreacted triethanolamine value of 14.6%.

MIX-7: C18 TEA Ester (3:1) Mix (80:20 Trans-/Cis-)

Methyl ester Mix-0-2 (293.0 g, 0.858 mol), base catalyst, andtriethanolamine (85.3 g, 0.572 mol) are charged to a 4-neck flaskequipped with a distillation head and condenser. The contents are heatedto 130° C. under a nitrogen flow (150 mL/min). Methanol distills as thereaction proceeds, and the temperature is gradually increased to 175° C.over 2 h. The nitrogen flow is then directed below the liquid surface.After 2 h at 175° C., the mixture is cooled. The methanol collected is62.0% of the theoretical amount. The mixture has become viscous and thereaction is deemed complete. The esteramine product, Mix-7, has anunreacted triethanolamine value of 0.99%.

C18-9: C18 MDEA Ester (2:1) Mix (100% Trans-)

Methyl ester C18-0 (258.2 g, 0.758 mol), base catalyst, andN-methyldiethanolamine (90.4 g, 0.758 mol) are charged to a 4-neck flaskunder a blanket of nitrogen. A subsurface sparge of nitrogen (175mL/min) is maintained. The mixture is stirred (170 rpm) and heatedwithout a vacuum to 130° C. and held for 1 h, after which thetemperature is increased to 150° C. and held for 3 h. Methanol evolvesrapidly, then slows. Additional N-methyldiethanolamine (0.68 g) is addedand heating continues at 170° C. (50 mm Hg) for 7 h, then at 180° C. (50mm Hg) for another 7 h. Because ¹H NMR analysis shows 35% of unreactedmethyl ester content, heating continues at 180° C. (760 mm Hg) foranother 70 h. NMR shows that the reaction is 93% complete. MoreN-methyldiethanolamine (5.5 g) is added, and the mixture is heated to180° C. and held overnight. After cooling, the esteramine product,C18-9, has an unreacted N-methyldiethanolamine value of 0.53%.

MIX-9: C18 MDEA Ester (2:1) Mix (80:20 Trans-/Cis-)

Methyl ester Mix-0-2 (266.0 g, 0.779 mol), base catalyst, andN-methyldiethanolamine (92.8 g, 0.779 mol) are charged to a 4-neck flaskunder a blanket of nitrogen. An above-surface sparge of nitrogen (50-75mL/min) is maintained. The mixture is stirred (170 rpm) and heatedwithout a vacuum to 130° C. and held for 6.75 h. The temperature isincreased gradually over 9 h to 175° C. and held at 175° C. (400 mm Hg)for 4 h, then at 175° C. (760 mm Hg) for 20.5 h. After cooling, theesteramine product, Mix-9, has an unreacted N-methyldiethanolamine valueof 1.25%.

MIX-11: C18 MDEA Ester (1:1) Mix (80:20 Trans-/cis-)

Methyl ester Mix-0-2 (186.4 g, 0.546 mol), base catalyst, andN-methyldiethanolamine (130.0 g, 1.09 mol) are charged to a 4-neck flaskunder a blanket of nitrogen. An above-surface sparge of nitrogen (50-75mL/min) is maintained. The mixture is stirred (170 rpm) and heatedwithout a vacuum with a gradual temperature ramp as follows: to 130° C.and held for 4.75 h; to 140° C. and held for 16.5 h; to 150° C. and heldfor 6.5 h; to 160° C. and held for 18 h. Thereafter, heating continuesat 170° C. for 8 h with a subsurface nitrogen sparge (50 to 75 mL/min).After cooling, the esteramine product, Mix-11, has an unreactedN-methyldiethanolamine value of 10.6%.

MIX-13: C18 MDEA Ester (3:1) Mix (80:20 Trans-/Cis-)

Methyl ester Mix-0-2 (311.0 g, 0.910 mol), base catalyst, andN-methyldiethanolamine (72.3 g, 0.607 mol) are charged to a 4-neck flaskunder a blanket of nitrogen. An above-surface sparge of nitrogen (50-75mL/min) is maintained. The mixture is stirred (170 rpm) and heated,initially without a vacuum, with a gradual temperature ramp as follows:to 130° C. and held for 6.5 h; to 140° C. and held for 2 h; to 150° C.and held for 2 h; to 160° C. and held for 1 h; to 170° C. and held for2.5 h; to 175° C. (400 mm Hg) and held for 2.5 h; to 175° C. (760 mm Hg)and held for 20.5 h; to 160° C. (760 mm Hg) and held for 16 h. Aftercooling, the esteramine product, Mix-13, has an unreactedN-methyldiethanolamine value of 0.45%.

MIX-67: C18 diFatty Acid (80:20 Trans-/cis-)

MIX-15: C18 diDMEA Ester Mix (80:20 Trans-/Cis-)

Fatty acid Mix-67 (170.7 g, 0.546 mol), prepared by hydrolysis of Mix-0,and N,N-dimethylethanolamine (175.3 g, 1.967 mol) are charged to a flaskequipped with a heating mantle, temperature controller, mechanicalagitator, nitrogen sparge, five-plate Oldershaw column, and condenser.The mixture is gradually heated to 145° C. while the overhead distillatetemperature is kept below 105° C. The reaction temperature is held at145-150° C. for 4 h, then increased over 2 h to 180° C., then held at180° C. overnight. The free fatty acid content is 3.30%, and thereaction is deemed complete. The mixture is cooled to 90° C. and theproduct is vacuum stripped (20 mm Hg, 0.5 h, then full vacuum, 1.5 h).The esteramine, Mix-15, has an unreacted dimethylethanolamine value of0.23% and gives a satisfactory ¹H NMR spectrum.

Ester Quat Formation from C18 and MIX C18 Esteramines

Each of the esteramines prepared as described above is quaternized asfollows. Table 4 summarizes the products, amount of dimethyl sulfate(“DMS,” quaternizing agent), reaction time, temperature, and amount ofisopropyl alcohol (“IPA”) solvent. The amount of DMS used for allreactions is determined by perchloric acid titration (“PAT” value) ofthe esteramine.

The esteramine is charged to a round-bottom flask equipped with a refluxcondenser, thermocouple/heating mantle, and nitrogen inlet. The sampleis heated to 50-65° C. if IPA is used to help solubilize the esteramine;otherwise, it is heated to 75-80° C. DMS is added dropwise via anaddition funnel. Temperature is kept at or below 70° C. if IPA isincluded and at or below 85° C. if it is not used. After the DMS isadded, the temperature is increased to 70° C. (if IPA is included) andstirred for 2-3 h; otherwise, the temperature is raised to 85° C. andstirred for 1 h. The reaction is considered complete if the PAT valueindicates <5% quaternizable amine remaining based on the original PATvalue of the esteramine. IPA (10-50 wt. %) is added (unless addedpreviously) to help eliminate residual DMS. The reaction mixture is alsoheated at 80-85° C. for 1-3 h to ensure complete DMS removal; contentsare also tested with a Dräger apparatus for residual DMS.

TABLE 4 C18 and MIX C18 Ester Quat Synthesis % Quat Rxn. by EsteramineDMS Time Temp. PAT IPA Ester Quat Product (g) (g) (h) (° C.) Value (g)

  MIX-4: C18 TEA Ester (2:1) Mix Quat 156.7 43.4 3 70 97.6 50.0

  MIX-6: C18 TEA Ester (1:1) Mix Quat 116.0 48.5 3 70 97.4 41.1

  MIX-8: C18 TEA Ester (3:1) Mix Quat 181.3 36.5 3 70 98.0 72.5

  C18-10: C18 MDEA Ester (2:1) Mix Quat 143.5 38.0 3 70 98.4 45.3

  MIX-10: C18 MDEA Ester (2:1) Mix Quat 146.7 37.5 3 70 98.5 35.0

  MIX-12: C18 MDEA Ester (1:1) Mix Quat 113.3 51.3 1 85 98.5 18.0

  +  

  MIX-14: C18 MDEA Ester (3:1) Mix Quat 186.3 36.3 1 80 98.0 39.3

  MIX-16: C18 diMEA DiQuat  91.8 46.6 2 70 97.8 30.0

Modified Triglyceride Based on Soybean Oil (“MTG-0”)

The procedures of Examples 1A and 1E are generally followed except that1-butene is omitted.

Mod. Triglyceride from Cross-Metathesis of Soybean Oil and 1-Butene(“UTG-0”)

The procedures of Examples 1A and 1E are generally followed to produceUTG-0 from soybean oil and 1-butene.

Modified Triglyceride Based on Palm Oil (“PMTG-0”)

The procedure used to make MTG-0 is followed, except that palm oil isused instead of soybean oil.

Mod. Triglyceride from Cross-Metathesis of Palm Oil and 1-Butene(“PUTG-0”)

The procedure used to make UTG-0 is followed, except that palm oil isused instead of soybean oil.

MTG-0 Feedstock Derivatives

TABLE 5 Summary of Modified and Unsaturated Triglyceride ProductsSoybean Oil Palm Oil Self-met. X-met. Self-met. X-met. MTG-0 UTG-0PMTG-0 PUTG-0 TEA Ester, 1:1 MTG-3 UTG-3 PMTG-3 PUTG-3 TEA Ester, 1:1quat MTG-7 UTG-7 PMTG-7 PUTG-7 TEA Ester, 2:1 MTG-1 UTG-1 PMTG-1 PUTG-1TEA Ester, 2:1 quat MTG-2 UTG-2 PMTG-2 PUTG-2 TEA Ester, 3:1 MTG-4 UTG-4PMTG-4 PUTG-4 TEA Ester, 3:1 quat MTG-8 UTG-8 PMTG-8 PUTG-8 MDEA Ester,2:1 MTG-9 UTG-9 PMTG-9 PUTG-9 MDEA Ester, 2:1 quat MTG-10 UTG-10 PMTG-10PUTG-10 TEA = triethanolamine; MDEA = N-methyldiethanolamine.Esteramines from Modified and Unsaturated Triglycerides: GeneralProcedure

Esteramines are prepared from modified triglycerides (MTG-0, PMTG-0) orunsaturated triglycerides (UTG-0, PUTG-0) using the following generalprocedure. Details of the preparation for the MTG products (MTG-1, -3,-4, and -9) appear in Table 6. The corresponding PMTG products areprepared analogously. Details of the preparation for the PUTG products(PUTG-1, -3, -4, and -9) also appear in Table 6, and the correspondingUTG products are prepared analogously.

In general, the triglyceride, alkanolamine (triethanolamine orN-methyldiethanolamine) and a base catalyst are combined in a 4-neckflask. The mixture is agitated (180 rpm) and heated rapidly to 175° C.under nitrogen. The mixture is allowed to react overnight and is thencooled to room temperature to give the esteramine. Residual unreactedalkanolamine is determined by titration of water-extractable amine withaqueous HCl. Amounts of reagents for selected esteramines appear inTable 6. The targeted product mixtures are also summarized below.

TABLE 6 Preparation of Esteramines from Modified or UnsaturatedTriglycerides residual Esteramine MTG-0, g PUTG-0, g TEA, g MDEA, galkanolamine, % MTG-1 230.6 — 70.4 — 3.88 MTG-3 187.2 — 112.7 — 14.2MTG-4 249.8 — 51.1 — 1.38 MTG-9 239.4 — — 60.6 3.88 PUTG-3 — 187.1 115.3— 14.3 PUTG-1 — 230.4 69.8 — 3.68 PUTG-4 — 249.7 50.6 — 1.33 PUTG-9 —239.3 — 59.8 2.84

MTG-1: MTG TEA Ester (2:1)

MTG-3: MTG TEA Ester (1:1)

MTG-4: MTG TEA Ester (3:1)

MTG-9: MTG MDEA Ester (2:1)

PUTG-3: PUTG TEA Ester (1:1)

PUTG-1: PUTG TEA Ester (2:1)

PUTG-4: PUTG TEA Ester (3:1)

PUTG-9: PUTG MDEA Ester (2:1)

Quaternization of Esteramines from Modified and UnsaturatedTriglycerides:

General Procedure

The esteramines prepared from modified or unsaturated triglycerides arequaternized using the following general procedure. Details of thepreparation for the MTG products (MTG-2, -7, -8, and -10) appear inTable 7. The corresponding PMTG products are prepared analogously.Details of the preparation for the PUTG products (PUTG-2, -7, -8, and-10) also appear in Table 7, and the corresponding UTG products areprepared analogously.

In general, the esteramine is charged to a round-bottom flask equippedwith a condenser, thermocouple, heating mantle, and nitrogen inlet, andthe contents are heated to 80° C. Dimethyl sulfate (“DMS”) is added viaaddition funnel. Enough DMS is added to achieve >95% quaternization asdetermined from the perchloric acid titration (PAT) value. After the DMSaddition, the temperature is raised to 85° C. One hour after the DMSaddition is complete, the % quaternization is ˜98%. Isopropyl alcohol(IPA) is added and the temperature is raised to 86° C. After 1 h, themixture is cooled to room temperature and the ester quat is removed andtested with a Dräger apparatus for residual DMS. For the PUTG-8preparation, the IPA is included in the initial charge, and the reactiontemperature is adjusted downward to 65° C.-70° C. accordingly. Amountsof reagents for selected ester quats appear in Table 7. The targetedproduct mixtures are also summarized below.

TABLE 7 Quaternization of Esteramines from Modified or UnsaturatedTriglycerides Ester Quat Esteramine Esteramine, g DMS, g IPA, g MTG-2MTG-1 143.1 27.4 19.1 MTG-7 MTG-3 138.9 43.2 20.2 MTG-8 MTG-4 141.2 19.417.8 MTG-10 MTG-9 147.6 29.4 19.7 UTG-2 UTG-1 157.3 32.1 21.0 PUTG-7PUTG-3 151.4 48.1 22.1 PUTG-2 PUTG-1 147.7 28.1 19.5 PUTG-8 PUTG-4 150.620.5 19.1 PUTG-10 PUTG-9 148.3 27.4 19.6

MTG-2 MTG TEA Ester (2:1) Quat

MTG-7: MTG TEA Ester (1:1) Quat

MTG-8: MTG TEA Ester (3:1) Quat

MTG-10: MTG MDEA Ester (2:1) Quat

PUTG-7: PUTG TEA Ester (1:1) Quat

PUTG-2 PUTG TEA Ester (2:1) Quat

PUTG-8: PUTG TEA Ester (3:1) Quat

PUTG-10: PUTG MDEA Ester (2:1) Quat

Water-Soluble Herbicide Formulation Testing

Surfactant candidates for water soluble herbicide applications areexamined as a replacement for the anionic, nonionic, or anionic/nonionicblend portion and compared to a known industry adjuvant standard for usein paraquat, a water soluble herbicide concentrate formulation. Astandard dilution test is conducted whereby the concentrates are dilutedin water to determine if solubility is complete.

Control:

Paraquat (9.13 g of 43.8% active material) is added to a 20-mL glassvial. A known industry paraquat adjuvant (2.8 g) is added and vigorouslymixed for 30 s. Deionized water (8.07 g) is added, and mixing resumesfor 30 s. Standard 342 ppm water (47.5 mL) is added to a 50-mL Nesslercylinder, which is stoppered and equilibrated in a 30° C. water bath.Once the test water equilibrates, the formulated paraquat (2.5 mL) isadded by pipette into the cylinder. The cylinder is stoppered andinverted ten times. Solubility is recorded as complete or incomplete.Cylinders are allowed to stand and the amount (in mL) and type ofseparation are recorded after 30 min., 1 h, 2 h, and 24 h. Results ofthe solubility testing appear in Table 8 below.

Anionic Test Sample:

Paraquat (4.57 g of 43.8% active material) is added to a 20-mL glassvial. An eight to ten mole alkyl phenol ethoxylate surfactant (0.7 g) isadded and vigorously mixed for 30 s. Test sample (0.7 g) is added andmixing resumes for 30 s. Deionized water (4.03 g) is added, and mixingresumes for 30 s. A 2.5-mL sample of the formulated paraquat is added to47.5 mL of 342 ppm hardness water, and testing continues as describedabove for the control sample.

Nonionic Test Sample:

Paraquat (4.57 g of 43.8% active material) is added to a 20-mL glassvial. Test sample (0.7 g) is added and vigorously mixed for 30 s. Sodiumlinear alkylbenzene sulfonate (“NaLAS,” 0.7 g) is added and mixingresumes for 30 s. Deionized water (4.03 g) is added, and mixing resumesfor 30 s. A 2.5-mL sample of the formulated paraquat is added to 47.5 mLof 342 ppm hardness water, and testing continues as described above forthe control sample.

Adjuvant (Anionic/Nonionic) Test Sample:

Paraquat (4.57 g of 43.8% active material) is added to a 20-mL glassvial. Test sample (1.4 g) is added and vigorously mixed for 30 s.Deionized water (4.03 g) is added, and mixing resumes for 30 s. A 2.5-mLsample of the formulated paraquat is added to 47.5 mL of 342 ppmhardness water, and testing continues as described above for the controlsample.

Criteria for emulsion solubility: Test samples should be as good as orbetter than the control with no separation after one hour. Three testsamples perform as well or better than the control in the emulsionstability test. Results appear in Table 8.

TABLE 8 Water Soluble Herbicide Formulation: Emulsion stability, mLseparation test Anionic Nonionic Adjuvant sample sol 1 h 24 h sol 1 h 24h sol 1 h 24 h Rating C10-7 S 0 0 S 0 0 S 0 0 good C12-7 S 0 0 D 0 0 S 00 good Mix-16 S 0 0 D Tr Tr S 0.25 0.25 good D = dispersable; S =soluble; I = insoluble; Tr = trace Control result: Solubility: D; 1 h: 0mL; 24 h: Tr.

Agricultural Dispersant Screening:

The potential of a composition for use as an agricultural dispersant isevaluated by its performance with five typical pesticide activeingredients: Atrazine, Chlorothalonil, Diuron, Imidacloprid andTebuconazole. The performance of each dispersant sample is evaluated incomparison with five standard Stepsperse® dispersants: DF-100, DF-200,DF-400, DF-500, and DF-600 (all products of Stepan Company), and each istested with and without a nonionic or anionic wetting agent. Overallresults versus the controls are summarized in Table 9; four esteraminesperform at least as well as the controls. Details of the individualtests are reported in Table 10 (wetting agent included) and Table 11 (nowetting agent). Note that sample C12-3 receives an overall rating of“good” when the results with and without the wetting agent are takeninto account.

A screening sample is prepared as shown below for each active. Wettingagents, clays, and various additives are included or excluded from thescreening process as needed. The weight percent of pesticide (“technicalmaterial”) in the formulation depends on the desired active level of thefinal product. The active level chosen is similar to other products onthe market. If this is a new active ingredient, then the highest activelevel is used.

Samples are evaluated in waters of varying hardness, in this case 342ppm and 1000 ppm. The initial evaluations are performed at ambienttemperature. Other temperatures can be evaluated as desired. The 342 ppmwater is made by dissolving anhydrous calcium chloride (0.304 g) andmagnesium chloride hexahydrate (0.139 g) in deionized water and dilutingto 1 L. The 1000 ppm water is made similarly using 0.89 g of calciumchloride and 0.40 g of magnesium chloride hexahydrate.

Technical material (60-92.5 wt. %), wetting agent (0.5-1.0 wt. % whenused), silica (0.5-1.0 wt. %), and clay (balance) are blended in asuitable container. The blend is milled to a particle size of at least ad (90) of <20μ using a hammer and air/jet mills as needed. Testdispersant (0.1 g) is added to test water (50 mL) in a beaker andstirred 1-2 min. Milled powder containing the technical material (1.0 g)is added to the dispersant solution and stirred until all powder is wet(2-5 min.). The mixture is transferred to a 100-mL cylinder usingadditional test water for rinsing the beaker and is then diluted tovolume. The cylinder is stoppered and inverted ten times, then allowedto stand. Visual inspection is performed at t=0.5, 1.0, 2.0, and 24hours, and the amount of sediment observed (in mL) is recorded. Trace ofsediment=“Tr” (see Tables 10-11).

TABLE 9 Overall Performance as an Agricultural Dispersant Sample RatingC10-5 Superior C12-3 Good C12-5 Good C12-7 Good Controls Good

TABLE 10 Agricultural Dispersants Testing: Nonionic or Anionic WettingAgent Included Sedimentation results at 1 h; 24 h (mL) test water,DF-200 DF-500 C12-3 C12-5 C12-7 ppm (anionic) (anionic) (nonionic)(nonionic) (anionic) Diuron 342 0.25-0.5; 1 Tr; 1 0.75; 1.25 0.5-1; 11.5; 2 1000 0.5-1; 1-1.25 2-2.5; 2 0.25-0.5; 0.75 0.5-1; 1 2.25; 2Chlorothalonil 342 0.25; 1.5 Tr; 1.25 0.5; 2 0.5; 1 Tr; 1 1000 Tr; 1.755; 3.5 Tr-0.5; 1-1.25 0.5; 1 Tr; 0.75 Imidacloprid 342 Tr; 1-1.5 Tr;1.5-2 Tr-0.25; 1 0.75-1; 1-1.5 1; 1.75-2 1000 Tr; 2 1-1.5; 3 Tr-0.25; 10.75-1; 2 0.5-1; 1.5-2 Tebuconazole 342 0; 1 Tr; 1 Tr; 0.5 Tr; 1 3; 3.51000 0.5-1; 3.5-4 12; 5 5.25; 3 Tr; 1 3.5; 3.5-3.75 Atrazine 342 Tr; 1Tr; 1 Tr-0.25; 1.5 0.25-0.5; 1-1.5 0.25-0.5; 1.75-2 1000 Tr; 2 7; 40.25; 1 0.5-1; 2 0.25-0.5; 1 Rating control control good good good

TABLE 11 Agricultural Dispersants Testing: No Wetting AgentSedimentation results at 1 h; 24 h (mL) test water, ppm DF-200 DF-500C10-5 C12-3 Diuron 342 1; 2 0.5; 1-1.5 0.25-0.5; 1 0.75-1; 1.5 1000 1;2-2.5 0.5-0.75; 2 0.25-0.5; 0.75-1 2.5-3; 2-2.5 Chlorothalonil 342 0.25;1-1.25 0.25; 1-1.25 0.25-0.5; 1.25-1.5 5-5.5; 4 1000 0.25-0.5; 1.25-1.52; 3 0.25-0.5; 1-1.25 5-5.25; 4 Imidacloprid 342 Tr; 1-1.5 0.5-1; 20.75-1; 1-1.25 0.5-0.75; 1.5-2 1000 Tr; 1-1.5 0.5-1; 2-2.5 0.5-0.75;1-1.25 2-2.25; 2 Tebuconazole 342 Tr; 1.25 Tr; 1.5 0; 0.25-0.5 0.5-0.75;2-2.5 1000 Tr; 3 Tr; 3 0; 0.5-0.75 5; 4.5-5 Atrazine 342 Tr-0.25; 1-1.50.5; 1 Tr-0.25; 0.75-1 1.5-2; 3 1000 Tr-0.25; 1-1.5 6; 3 Tr-0.25; 0.75-13; 4 Rating control control superior inferior

Hard-Surface Cleaners: Aqueous Degreasers

This test measures the ability of a cleaning product to remove a greasydirt soil from a white vinyl tile. The test is automated and uses anindustry standard Gardner Straight Line Washability Apparatus. A cameraand controlled lighting are used to take a live video of the cleaningprocess. The machine uses a sponge wetted with a known amount of testproduct. As the machine wipes the sponge across the soiled tile, thevideo records the result, from which a cleaning percentage can bedetermined. A total of 10 strokes are made using test formulationdiluted 1:32 with water, and cleaning is calculated for each of strokes1-10 to provide a profile of the cleaning efficiency of the product. Thetest sample is used as a component of different control formulationsdepending on whether it anionic, amphoteric, or nonionic.

A neutral, dilutable all-purpose cleaner is prepared from propyleneglycol n-propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate(4.0 g), Stepanol® WA-Extra PCK (sodium lauryl sulfate, Stepan, 1.0 g),test sample (0.90 g if 100% active material), and deionized water (to100.0 g solution). The control sample for nonionic/amphoteric testingreplaces the test sample with Bio-Soft® EC-690 (ethoxylated alcohol,Stepan, 1.0 g, nominally 90% active material).

Soil Composition:

Tiles are soiled with a particulate medium (50 mg) and an oil medium (5drops). The particulate medium is composed of (in parts by weight)hyperhumus (39), paraffin oil (1), used motor oil (1.5), Portland cement(17.7), silica 1 (8), molacca black (1.5), iron oxide (0.3), bandy blackclay (18), stearic acid (2), and oleic acid (2). The oil medium iscomposed of kerosene (12), Stoddard solvent (12), paraffin oil (1),SAE-10 motor oil (1), Crisco® shortening (product of J. M. SmuckerCompany) (1), olive oil (3), linoleic acid (3), and squalene (3).

Four samples, Mix-3, Mix-5, Mix-15, and UTG-7, perform equal to theircorresponding controls in this test (see Tables 12A and 12B).

TABLE 12A Control Runs for Gardner Straight Line Washability Test Ave. %clean after 2, 4, 6, 8, or 10 swipes 2 4 6 8 10 Control 4 52.5 58.2 59.560.9 63.3 Control 18 62.2 67.6 70.4 71.7 71.7 Control 19 60.8 68.0 70.671.4 71.5

TABLE 12B Nonionic/Amphoteric Test Samples: Inventive Examples Com- Con.pound Ave. % clean Sample # class 2 4 6 8 10 Rating Mix-3 19 TEA ester55.0 61.6 63.3 65.6 66.7 equal Mix-5 4 TEA ester 60.1 62.0 64.7 66.367.1 equal Mix-15 18 DMEA 47.0 60.9 62.8 64.3 65.5 equal ester UTG-7 4TEA ester 59.5 62.7 63.7 66.0 66.4 equal quat

Hair Conditioners: Procedure for Evaluation of Wet Combability

Hair tresses (10″ lengths, 2-3 g) are prepared using a consistent anduniform hair type (double-bleached, blond). The tresses are collectivelyshampooed with a 15% active sodium lauryl sulfate solution. Care istaken to avoid excessive tangling during shampooing. The tresses arerinsed clean with 40° C. tap water. The process is repeated to simulatea double shampoo application. The tresses are separated and tagged fortesting. The conditioner preparation (2.0 cm³), whether it be the testor the control, is applied to each clean, wet tress using a syringe.When the test material is an unquaternized esteramine, the baseconditioner used as a control for the testing contains cetyl alcohol(2.0%), hydroxyethyl cellulose (0.7%), cetrimonium chloride (1.0%),potassium chloride (0.5%), and water (qs to 100%). The unquaternizedesteramine is formulated as a 2 wt. % (actives) additive to the baseconditioner. When the test material is a quaternized esteramine, theconditioner used as a control for testing contains cetyl alcohol (3%),cetrimonium chloride (1%), and water (qs to 100%). The quaternizedesteramine is formulated at 1% active into a conditioner that containscetyl alcohol (3%) and water (qs to 100%).

The conditioner is worked through the hair for one minute with downwardfinger strokes. The tresses are rinsed thoroughly clean under 40° C. tapwater. Excess water is squeezed from each tress to simulate towel-dryhair. The hair is combed through, at first, in the wet state. Ease ofcombing is evaluated for the test samples and the base or controlconditioner, and qualitative ratings are assigned to the test samples incomparison to the results with base or control conditioner only.

When the material is an unquaternized esteramine, enhancement ofconditioning of the base by the esteramine additive is the technicalsuccess criteria at this stage and is the basis for a superior rating.Equal to lower performance versus the base conditioner earns an inferiorrating.

When the material is a quaternized esteramine, the rating system is asfollows: “superior” is an improvement of wet combing above that of theconditioner used as a control for testing; “equal” is wet combingcomparable to the conditioner used as a control for testing; and“inferior” is wet combing worse than the conditioner used as a controlfor testing. Results appear in Table 13.

TABLE 13 Wet Combability Performance in Hair Conditioners Superior GoodMTG-1 PUTG-1 Base conditioner UTG-4 PUTG-4 PMTG-7* PMTG-1 PUTG-7* PMTG-4PUTG-9 PMTG-9 *quaternized esteramines

Personal Care: Cleansing Application

Viscosity and mechanical shake foam tests are used to assess the likelyvalue of a particular surfactant as a secondary surfactant in cleansingapplications for personal care.

All experimental samples are evaluated for their performance versus acontrol (either cocamide MEA or cocamidopropylbetaine).

Viscosity curves are generated by preparing aqueous solutions of thetest material or the control with 12% active sodium lauryl ether (1)sulfate (SLES-1), then measuring viscosity by means of a BrookfieldDV-1+ viscometer. The active contents of test material are 1.5% if thematerial is an amidoamine, and 3% if the material is an amidoamineoxide. Sodium chloride is added incrementally (1-3 wt. %) and viscosityis recorded as a function of increasing NaCl concentration. A “good”result is a curve that shows a viscosity build comparable to the controlsample. A “superior” rating indicates that the sample builds viscositysubstantially more rapidly than the control.

Foaming properties are evaluated using a mechanical shake foam test.Aqueous solutions composed of 12% active SLES-1 and the test material orcontrol (1.5% active content if material is an amidoamine, 3% activecontent if material is an amidoamine oxide) are prepared. Samplesolutions calculated at 0.2% total surfactant active are thereafter madefrom the aqueous solutions using 25° C. tap water. A 100.0-g portion ofthe solution is carefully transferred to a 500-mL graduated cylinder.Castor oil (2.0 g) is added. The cylinder is stoppered and mechanicallyinverted ten times, then allowed to settle for 15 s. Foam height isrecorded. After 5 min., foam height is recorded again. The experiment isrepeated without the castor oil. In one set of experiments, thecleansing base contains SLES-1 in both the experimental and controlruns. In a second set of experiments, the cleansing base containsanother widely used anionic surfactant, i.e., a mixture of sodium methyl2-sulfolaurate and disodium 2-sulfolaurate, instead of SLES-1. A “good”result is recorded when the solution containing the test materialresults in foam heights that are within +/−25 mL of the control runs.Results >25 mL of the control garner a superior rating; results <25 mLof the control are rated inferior.

MTG-1, when tested against cocamidopropyl betaine, demonstrates equalfoaming and viscosity building properties, and is rated “good” overall.

Personal Care/Antibacterial Handsoap: Method to Determine FoamEnhancement Benefit

Foam volume, which signals “clean” to consumers, is a desirableattribute in an antibacterial handsoap. Because cationic antibacterialactives are not compatible with anionic surfactants (the best foamers),achieving sufficient foam volume with them is challenging. The methodbelow identifies surfactants that provide more foam volume thancocamidopropylbetaine (actives/actives basis) in an antibacterialhandsoap base. Formulation: deionized water (q.s. to 100 wt. %),cocoglucoside (3.0 wt. %), lauramine oxide (3.0 wt. %), benzalkoniumchloride (0.1 wt. %), and test molecule or cocamidopropylbetaine (3.0wt. %).

Solutions are prepared by combining ingredients in the order prescribedabove, stirring with a stir bar or mixing gently using an overheadstirrer or manually using a spatula. Heat may be applied if the testmolecule is a solid at room temperature. Mixing is maintained to ensurea homogenous solution. The pH is adjusted to 6.5+/−0.5.

Test and control solutions are compared, with and without 2% castor oil,at 0.2% total surfactant active concentration (2.22 g solution to 100 mLwith tap water from Lake Michigan, ˜150 ppm Ca/Mg hardness) for foamvolume using the cylinder inversion test. Initial and delayed (5 min.)measurements are taken.

Rating system: Superior: a result >25 mL over the cocamidopropylbetainecontrol in both oil and no-oil systems. Good: a result within 25 mL ofthe cocamidopropylbetaine control in both oil and no-oil systems.Inferior: a result >25 mL below that of the cocamidopropylbetainecontrol in both oil and no-oil systems.

Compared with the controls, three samples, C10-5, C12-7, and UTG-2 allshow good overall performance in the antibacterial handsoap tests.

Oilfield Corrosion Inhibition: Polarization Resistance Procedure

Polarization resistance is run in dilute NACE brine (3.5 wt. % NaCl;0.111 wt. % CaCl₂.2H₂O; 0.068 wt. % MgCl₂.6H₂O) under sweet conditions(CO₂ sparged) at 50° C. The working electrode is cylindrical, made ofC1018 steel, and rotates at 3000 rpm. The counter electrode is aplatinum wire. The reference is a calomel electrode with an internalsalt bridge. A baseline corrosion rate is established over at least a3-h period. Once the baseline has been established, the corrosioninhibitor is injected and data is collected for the remainder of thetest period. The desired inhibitor concentration is 0.00011-0.0010 meq/gactive. Software details: initial delay is on at 1800 s with 0.05 mV/sstability; range: −0.02 to +0.02V; scan rate: 0.1 mV/s; sample period: 1s; data collection: ˜24 h. The final corrosion rate is an average of thelast 5-6 h of data collection. Protection rate is calculated from:

${{Protection}\mspace{14mu} {Rate}} = \frac{\begin{matrix}\left( {{{Initial}\mspace{14mu} {Protection}\mspace{14mu} {{Rate}\left\lbrack {{no}\mspace{14mu} {inhibitor}} \right\rbrack}} -} \right. \\{\left. {{Final}\mspace{14mu} {Protection}\mspace{14mu} {{Rate}\mspace{14mu}\left\lbrack {{with}\mspace{14mu} {inhibitor}} \right\rbrack}} \right)*100}\end{matrix}}{\left( {{Initial}\mspace{14mu} {Protection}\mspace{14mu} {{Rate}\mspace{14mu}\left\lbrack {{no}\mspace{14mu} {inhibitor}} \right\rbrack}} \right)}$

As shown in Table 14, twenty-one of the tested samples show overallperformance as corrosion inhibitors that equals or exceeds that of thecontrol.

TABLE 14 Performance in EOR Corrosion Inhibitors Protection Rate (%)Sample Low Dose Mid Dose High Dose Overall Rating Industry Std. A 85 8580 Control B 66 83 76 Control C 97 98 97 Control D 90 98 85 C10-5 90 7261 good C12-5 80 89 90 good C16-7 80 73 78 good Mix-4 84 88 89 goodMix-6 91 90 80 good Mix-10 79 85 82 good MTG-2 59 95 89 good MTG-7 80 8981 good MTG-8 16 77 95 good MTG-10 72 72 50 good PMTG-2 71 85 90 goodPMTG-7 98 84 73 good PMTG-8 96 98 99 good PMTG-10 93 85 89 good UTG-2 9591 89 good UTG-7 92 86 90 good UTG-10 87 95 93 superior PUTG-2 93 91 90good PUTG-7 94 87 63 good PUTG-8 71 90 83 good PUTG-10 94 76 70 good

The preceding examples are meant only as illustrations. The followingclaims define the invention.

1. An esteramine or an esteramine derivative made by one or more ofquaternizing, sulfonating, alkoxylating, sulfating, or sulfitating theesteramine, wherein the esteramine comprises a reaction product of ametathesis-derived C₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioicacid, or their ester derivatives with a tertiary alkanolamine; saidesteramine having the formula:(R¹)_(3-m)—N—[(CH₂)_(n)—(CHCH₃)_(z)—O—CO—R²]_(m) where: R¹ is C₁-C₆alkyl; R² is —(CH₂)₇—CH═CHR³ or —(CH₂)₇—CH═CH—(CH₂)₇—CO₂R⁴; R³ ishydrogen or C₁-C₇ alkyl; R⁴ is substituted or unsubstituted alkyl, aryl,alkenyl, oxyalkylene, polyoxyalkylene, glyceryl ester, or a mono- ordivalent cation; m=1-3; n=1-4; z=0 or 1; and when z=0, n=2-4; andwherein when R³ is C₁-C₇alkyl, the acid or ester derivative reactant hasat least 25 mole % of trans-Δ⁹ unsaturation.
 2. (canceled)
 3. Theesteramine or esteramine derivative of claim 1 wherein the acid or esterderivative reactant has at least 50 mole % of trans-Δ⁹ unsaturation. 4.The esteramine or esteramine derivative of claim 1 wherein thealkanolamine is selected from the group consisting of triethanolamine,N-methyldiethanolamine, N,N-dimethylethanolamine, and alkoxylatedderivatives thereof.
 5. (canceled)
 6. The esteramine or esteraminederivative of claim 1 wherein the ester derivative is a modifiedtriglyceride made by self-metathesis of a natural oil.
 7. The esteramineor esteramine derivative of claim 6 wherein the natural oil is selectedfrom the group consisting of soybean oil, palm oil, rapeseed oil, algaloil, and mixtures thereof.
 8. (canceled)
 9. The esteramine or esteraminederivative of claim 1 wherein the ester derivative is an unsaturatedtriglyceride made by cross-metathesis of a natural oil with an olefin.10. The esteramine or esteramine derivative of claim 9 wherein thenatural oil is selected from the group consisting of soybean oil, palmoil, rapeseed oil, algal oil, and mixtures thereof, and the olefin is aC₂-C₈ α-olefin or a C₄-C₉ internal olefin.
 11. (canceled)
 12. Theesteramine or esteramine derivative of claim 1 wherein the equivalentratio of acyl groups in the metathesis-derived C₁₀-C₁₇ monounsaturatedacid, octadecene-1,18-dioic acid, or ester derivative to hydroxyl groupsin the tertiary alkanolamine is within the range of 0.1 to
 3. 13. Theesteramine or esteramine derivative of claim 12 wherein the equivalentratio of acyl groups to hydroxyl groups is within the range of 0.3 to 1.14. The esteramine or esteramine derivative of claim 1 wherein theC₁₀-C₁₇ monounsaturated acid or ester derivative comprises a C₁₀ and aC₁₂ monounsaturated acid or ester derivative.
 15. The esteramine oresteramine derivative of claim 1 wherein the C₁₀-C₁₇ monounsaturatedacid or ester derivative comprises a C₁₀ and a C₁₄ monounsaturated acidor ester derivative.
 16. The esteramine of or esteramine derivativeclaim 1 wherein the C₁₀-C₁₇ monounsaturated acid or ester derivativecomprises a C₁₀ and a C₁₆ monounsaturated acid or ester derivative.17-28. (canceled)